Antistatic fiber containing chain-extended tetrols based on diamines

ABSTRACT

WHEREIN X&#39;&#39; HAS A VALUE FROM 1 TO 6 AND Y&#39;&#39; HAS A VALUE OF 1 TO 6 IS ADDED.   IN WHICH R is   IN WHICH X HAS A VALUE OF FROM 1 TO 6 AND Y HAS A VALUE OF FROM 6 TO 30; AND   AN ADDITIONAL SMALL PROPORTION OF A HINDERED PHENOL REPRESENTED BY THE FORMULAE:   AND AT LEAST ONE COMPOUND SELECTED FROM THE GROUP CONSISTING OF DIEPOXIDES AND COMPOUNDS WHICH YIELD THE FOLLOWING DIVALENT RADICALS:   A antistatic properties of fibers of polyamide could be improved by dispersing in the polyamide a small proportion of a reaction product of a tetrol compound represented by the formula:

the following divalent radicals:

States Patent [1 1 [11] 3,873,639

Crescentini et al. Mar. 25, 1975 l l ANTlSTATIC FHBER CONTAINING 9 ECHAIN-EXTENDED TETROLS BASED ON I DIAMINES I (Z-A [75] Inventors:Lamberto Crescentini; Rodney Lee f Wells, both of Chester, Va. O o [73]Assignee: Allied Chemical Corporation, H H

Morristown, NJ. [22] Filed: Jul 12, 1972 an additional small proportionof a hindered phenol A l N 271316 represented by the formulae:

(lower) alkyl [52] US. Cl.260/857 PG, 260/4585 B, 260/4585 P, 260/75 N,260/775 AM, 260/775 AQ,

260/78 SC, 260/830 P [51] Int. Cl C08g 41/04 [58] Field of Search.260/857 PG, 45.85 B, 45.85 P

(lower) alkyl [56] References Cited UNITED STATES PATENTS in which has avalue of from 1 to 6 and v has a value 3,285,855 ll/l966 Dexter 260/4585S f from 6 [Q 30; 11nd 3,330,859 7/l967 Dexter 260/4585 B Y 3,364.250l/l968 Dexter 260/4585 B R 3,594,448 v um Birenzvige... 260/4585 B3,644,482 2/l972 Dexter 260/4585 B C 3,657,386 4/1972 WCCtlOn... 260/857PG 3,723,489 3/1973 Dexter 260/4585 B 3,723,503 3/l973 Dexter 260/4585 Bin which R is Primary Examiner-Paul Lieberman (lower) alkyl Attorney,Agent, or FirmFred L. Kelly 0 II [57] ABSTRACT H (CH (CH A antistaticproperties of fibers of polyamide could be 2 2 Y' improved by dispersingin the polyamide a small proportion of a reaction product of a tetrolcompound represented by the formula: e lkyl H3 (1H l-I (OCI'IZCHZ) a(0CHCH b\ (CH2CHO) C (CH CH O) H CH N"A"N CH I I 3 H(OCH CH2) (OCHCH(CH2CHO)g(CH CH2O) H and at least one compound selected from the groupwherein x has a value from 1 to 6 and y has a value consisting ofdiepoxides and compounds which yield of l to 6 is added.

10 Claims, N0 Drawings ANTISTATIC FIBER CONTAINING CHAIN-EXTENDEDTETROLS BASED ON DIAMINES CROSS REFERENCE TO RELATED APPLICATION Thisapplication is directed to an improvement upon the invention disclosedin U.S. application Ser. No. 239,905, filed Mar. 31, 1972, nowabandoned. U.S. application Ser. No. 239,905 is hereby incorporated byreference into this application.

BACKGROUND OF THE INVENTION This invention relates to a process for themeltspinning of a filamentary structure from a synthetic polyamidepolymer. More particularly, it is concerned with an improved process forthe formation of an improved antistatic filament, yarn or the like bymelt-spinning a synthetic linear fiber-forming polyamide.

It has been suggested that the utility of synthetic fibers could beincreased and their properties, in particular their antistaticproperties, could be improved if a polyalkylene ether ofhigh molecularweight is included in the polymer. More specifically, it is disclosed inU.S. Pat. No. 3,475,898 to Magat and Sharkey to usepoly(ethylenepropylene) ether glycols for this purpose. More recently,U.S. Pat. No. 3,657,386 discloses that certain propylene oxideethyleneoxide copolymers based on ethylene diamine are useful in preparation ofan antistatic fiber of polyamide. It has also been suggested that theutility of synthetic fiber of polyamide could be increased by dispersingin the polyamide an antistatic compound which is a reaction product of:

H CH 9 H(OCH CH (OCHCH CH "N CH I I H(OCH2CH2) locttca where a, b, c, a,e,f, g, and h are each a whole number and A is a difuntional radicalfrom a hydrocarbon conuse of this antistatic agent, serious problemswere encountered in meltspinning due to the frequent occurrence of nubsin the fiber. The term "nubs is conventionally applied and is usedherein to mean enlarged selections of filament no more than severalfilament 65 dimeters in length. Nubs may be formed by a foreign.non-orientable substance which interferes with normal fiber stretch in ashort section, resulting in an enlarge- (CI-I CHOM ment. Foreignsubstances which are believed to have contributed to nubs in the presentinstance include carbonized polymer from face of extruder die andspinnerette, and gels formed in the polymer. Gels appear to be the chiefcause, i.e., the nubs are probably created by non-orientable gel fromcross-linked polymer. Thermal degradation ofthe polymer may be animportant causative factor.

The reactions in thermal degradation of polyamides containingpolyalkylene ether additives are not entirely understood. It is likelythat thermal degradation produces a decomposition product which servesto form cross-links between amide groups and adjacent polymer chains.The decomposition reaction proceeds slowly, finally building up athree-dimensional network of molecules which may be called polymer geland which eventually reaches the stage where it forms an .infusiblecoating on the walls of the reactor and other equipment.

A serious difficulty which arises from the formation of this polymer gelon the interior walls is that from time to time pieces break off and getinto the flowing polymer stream where they produce damage to thespinning equipment.

The greatest difficulty, however, is caused by polymer gel which hasprogressed to the three-dimensional structural stage, but which has notyet reached the stage of being infusible. This kind of polymer gel isreadily carried with the stream of flowing polymer. Being still moltenor at least softened, it passes through the pump and even through thefilter medium to show up either as discontinuities or as viscositydifferences in (CH' CH O) H (cn ca oi tt the spun filament. When thesefilaments are later cold drawn, these defects may cause breaks in thefilaments which either cause the whole thread to break or else form nubswhich go throught to be counted'as quality defects in the final yarns.

SUMMARY OF THE INVENTION It is an object of this invention to avoid theabove difficulties by minimizing gel formations in the molten polyamide.Another object is to avoid accumulation of polymer gel on the wallsofthe reactor, in the pump, or in the filtering medium whenmelt-spinning the polyamide. A further object is to improve theuniformity and quality of filaments or fibers formed from the moltenpolymer, in particular to minimize nub formation in the filaments. Otherobjects will become apparent from the disclosure and the appendedclaims.

These objects are accomplished by the present invention which providesan improvement in the process for the formation of an antistaticpolyamide fiber from a fiber-forming polyamide polymer containing about1 percent to 12 percent by weight of an antistatic compound which is areaction product of a tetrol compound represented by the formula:

-C-A -C- and where A is a difunctional radical from a hydrocarboncontaining 1 to 30 carbon atoms, by extruding the molten polymer throughan orifice into a quenching medium and thereafter stretching theresulting filaments, the improvement comprising dissolving in theextrudate prior to extrusion at least 0.1 percent by weight, preferably0.5 to 8 percent, based on the weight of the antistatic compound, of aphenol of the formulae:

(lower) alkyl (lower) alkyl in which has a value of from 1 to 6 and vhas a value of from 6 to 30; and

in which R is (loweltl alley].

II H0 (cH2) c"0" (lower) alkyl 3 4 9 3 E 3 H (OCH CH (OCHCH /(CH CHO) c(CH CH O) H CH N-A-N CH I I II tocrt cttzt I I (CH CHO g CH CH O) Hwhere a, b, c, d, e,f, g, and h are each a whole number (C H COOR" and Ais a difunctional radical from a hydrocarbon con- 10 2n taining l to 13carbon atoms, said tetrol compound S having a molecular weight betweenabout 4,000 and about 50,000 and at least one compound selected from C HCOOR" the group consisting of diepoxides and compounds which W thefOhOWlhg divalent radlcalsi 15 wherein R" is an alkyl radical containing8 to 18 carbon atoms and n is l to 3. 0 0 As stated above, the presentinvention is an improve- II II ment upon the invention disclosed in U.S.application Ser. No. 239,905 which relates to an antistatic fibercontaining a novel antistatic compound. The novel antistatic compound isprepared by reacting a tetrol compound, as described above, with achain-extender compound, for example a diepoxide, a dicarboxylic acid ordialkyl ester thereof, or a diisocyanate, to form'predominantlybranched, chain-extended polymer having a melt viscosity of about 800 to50,000 centipoises, preferably 1,500 to 25,000 centipoises, at 100C.Preferably, the ethylene oxide moiety makes up 10 to of the molecularweight of the antistatic compound. The mol ratio of chain-extendercompound to tetrol compound is preferably between about 0.7 and 1.0.

The alkylated phenol compounds useful in the present invention are knowncompounds and some are commercially available. The alkylation of phenolsis readily conducted with a variety of catalysts and alkylating agents;sec Price, Organic Reactions Ill, 58 (1946). The preparation of2,6-dialkylphenols by direct alkylation is relatively difficult but aprocedure is furnished .in Journal of Organic Chemistry, 2!. 712 (1956).Pertinent patents include U.S. Pat. Nos. 3,285,855 and 3,330,859. Thesulfur compounds of the invention may be prepared in accordance withChemical Abstracts, 64, 3362C. U.S. Pat. No. 2,762,836 is alsopertinent.

The tetrol compound which is chain-extended for use as an antistaticadditive in this invention is fully described in U.S. Pat. No. 2,979,528to Lundsted, assignor to Wyandotte. Suitable tetrol compounds arecommercially available under the trademark Tetronic as a series ofpoly(oxyethylene)poly(oxypropylene) block copolymers having molecularweights from 1,650 to over 26,000. This series varies in length ofpoly(oxyethylene) chain and poly(oxypropylene) chain. A 3 and 4 digitcode number indicates the molecular composition. When four digits areemployed, the first two explain the average molecular weight of thehydrophobc (poly(oxypropylene) branches on the alkylenediamine). Whenthree digits are used only the first number serves this purpose. Thelast digit of each code number represents the weight percentage ofhydrophilic (poly(oxyethylene)) units to the nearest 10%. The tetrolcompounds in the examples are described this way.

As diamines upon which the tetrols are based, in ad dition to ethylenediamine, diamines of a hydrocarbon containing 1 to 13 carbon atoms,preferably the lower alkyl diamines, where the lower alkyl radicalcontains l-6 carbon atoms, can be used.

The polyepoxy coupled compounds can be prepared by the method taught inBritish Pat. No. 793,915, Example I. The other classes of compound canbe similarly prepared, as in Example 10, in U.S. Pat. No. 3,009,884.

Typical of the acids and their esters to provide the chain extendingdifunctional radical are the dialkyl plithalic, isophthalic orterephthalic esters, such as dimethyl terephthalate and adipic,phthalic, terephthalic, sebacic, glutaric, pimelic, isocinchomeronicacids and their esters.

Typical of the polyepoxy compounds which provide the difunctional ordivalent compounds, used to chain extend the tetrols based on diamines,are those polyepoxy compounds described in British specification No.793,915 to Union Carbide on page 2, line 48 to line 121.

Also useful to form chain-extending divalent radicals are the aromaticor aliphatic diisocyanates, having a structure OCN -A-NQO, where A isdefined as above.

The antistatic fiber of this invention may also contain conventionalfiber additives such as antioxidants, stabilizers, delusterants, dyeingassists, and colorants.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The invention will now befurther described in the following specific examples which are to beregarded solely as illustrative and not as restricting the scope of theinvention.

EXAM PLE 1 This example shows a method of preparing a preferredantistatic additive of the type disclosed in U.S. application Ser. No.239,905,1'iled Mar. 31, 1972. The

C H CH-CH O instant h nxt ns sipelymer.i prepa d r m? rol compoundcovered by U.S. Pat. No. 2,979,528 to Lundsted, and sold commercially asTetronic 1504.

Three hundred grams of Tetronic 1504 (molecular weight 12,500) wasplaced in a three-neck flask fitted- EXAMPLE 2 This example shows amethod of preparing a preferred antistatic additive of the typedisclosed in U.S.

6 application Ser. No. 239,905, filed Mar. 31, 1972. The instantchain-extended polymer is prepared from a tetrol compound covered byU.S. Pat. No. 2,979,528 to Lundsted, and sold commercially as Tetronic1504.

Three-hundred grams of Tetronic 1504 (molecular weight 12,500) wasplaced in a three-neck flask fitted with a thermometer. stirrer. andadditional funnel. The Tetronic 1504 was stirred and heated to C. and5.7 grams of 4,4 methylene bis (cyclohexyl) isocyanatc.

(molecular weight 262.4) was added dropwise to the material in theflask. Agitation was continued for 1 hour at 10(1l()5C. after theaddition was completed. Then the product was cooled to room temperature.It was a soft solid having a melt viscosity of 8,300 centipoises at100C. measured with the Brookfield viscometer. The viscosity of theoriginal Tetroinic 1504 was 200 centipoises at 100C.

EXAMPLE 3 This example shows a method of preparing a preferredantistatic additive of the type disclosed in U.S. application Ser. No.239,905 filed Mar. 31, 1972. The instant chainextended polymer isprepared from a tetrol compound covered by U.S. Pat. No. 2,979,528 toLundsted, and sold commercially as Tetronic 1504.

Three hundred grams of Tetronic 1504 (molecular weight 12,500) wasplaced in a three-neck flask fitted with a thermometer. stirrer, andaddition funnel. The Tetronic 1504 was stirred and heated to C, and 7.4grams of diglycidyl ether of 2,2-bis(4-hydroxyphenyl)-propane of thestructure:

(molecular weight 340.4) was added to the material in the flask.Agitation was continued for 2.5 hours at C. 'after the addition wascompleted. Then the product was cooled to room temperature. It was asoft solid having a melt viscosity of 6.000 centipoises at 100C.measured with the Brookfield viscometer. The viscosity of the originalTetronic 1504 was 200 centipoises at 100C.

EXAMPLE 4 A glass reactor equipped with a heater and stirrer was chargedwith a mixture of 1,520 grams of ecaprolactam and 80 grams ofaminocaproic acid. The mixture was then flushed with nitrogen and wasstirred and heated to 255C. over a 1 hour period at atmospheric pressureto produce a polymerization reaction. The heating and stirring wascontinued at atmospheric pressure under a nitrogen sweep for anadditional 4 hours in order to complete the polymerization. During thelast 30 minutes of the polymerization, 2.7 grams of tetra[methylene3-(3,,5-di-tertiary-butyl-4'-hydroxyphenyl)propionate]methane and 90grams of the antistatic compound of Example 1, were added to thepolycaproamide and stirring was continued to thoroughly mix theadditives throughout the polymer. The tetralmethylene3-(3,5'-di-tertiary-butyl-4-hydroxyphenyl)propionate]methane is solidcommercially under the tradename lrganox 1010 and has the formula:

c (CH3) 3 c CH2O-CCH2'-CH2 OH C (CH3) Nitrogen was then admitted to theglass reactor and a small pressure was maintained while the polymer wasextruded from the glass reactor in the form of a polymer ribbon. Thepolymer ribbon was subsequently cooled. pelletized, washed and thendried. The polymer was a white solid having a relative viscosity ofabout 55 to 60 as determined by a concentration of l 1 grams of polymerin 100 milliliters of 90% formic acid at 25C. (ASTMD-789-62T).

The polycaproamide pellets containing the antistatic agent and otheradditives were melted at about 285C. and then melt-extruded under apressure of about 1,500 psig through a l6-orifice spinnerette, each ofthe orifices having a diameter of 0.014 inch, to produce a 250-denierfiber. The fiber was then collected at about 1,000 feet per minute andwas drawn about 3.5 times its extruded length to produce a 70-denieryarn. For convenience, this yarn hereinafter will be called Yarn A. Acontrol yarn containing the antistatic agent but no.

additional additives was producedin the same manner as described above.For convenience, this yarn hereinafter will be called YarnB.

Yarn A and Yarn B were woven into conventional plain weave fabrics. Thefabrics were cut into fabric test samples having a width of 3 inches anda length of 9 inches. The fabric samples were tested for theirantistatic property in accordance with the general procedure describedin the Technical Manual oft/1e American Association of Textile Chenzisls and Colorists, 1969 edition. Volume 45, at pages 206-207. Thistest procedure is entitled Electrostatic Clinging of Fabrics: Fabric toMetal Test and is numbered AATCC 115-1969. In accordance with thiselectrostatic test, Yarn A and Yarn B both showed excellent antistaticproperties for example, average time for fabric samples to decling frommetal completely on their own was about 120 seconds after 25 washcycles. Yarn A and Yarn B- were also tested for the number of nubs perpounds as shown in Example 5.

EXAMPLE This example outlines the method used for locating, dentifyingand calculating the nubs per pound in Yarn A and Yarn B as prepared inExample 4. In this method 1 nub is defined as an enlarged place in afilament which is no more than several filament diameters in length.This method may be used for either monofilamentor multifilament yarns;however, it is not applicable to most types of crimped yarn.

In accordance with the test, the -denier yarn is drawn directly from thepackage by means of an air aspirator and is passed through an opening ofknown width, specifically, 0.0030 inch in width. Such an opening isconveniently provided by use a ceramic cleaner gap, which is wellknownin the art. The presence of a nub is detected when it stops the yarnpassage through the opening. The filaments are separated and the causeof the yarn stopping identified as a nub or as the twisted end of abroken filament. For representative results, about grams of yarn ispassed through the gap and the number of nubs counted. Table 1 belowshows the results of testing on Yarn A and Yarn B.

TABLE I Determination of Nubs per Pound Yarn Nub Count Pcr Sample Poundof Yarn Yarn A 1,463 Yarn B 4,257

It will be noted that the addition of only antistatic compound to thepolyamide caused the nub count to increase to 4,257 per pound of yarn,which is much higher than ordinary polyamide fiber. However. theaddition of the antistatic compound plus the phenol compound reduced thenub count to 1,463 nubs per pound of yarn.

EXAMPLE 6 (ca l c CI'I CH COOC H 7 EXAMPLE 7 EXAMPLE 8 The procedure ofExample 4 (Yarn A) was followed except that grams ofthe antistaticadditive of Example 2 was used together with 2.7 grams oftetra[methylene 3-(3,5'di-t-butyl-4-hydroxyphenyl)propionatelmethane.The fiber produced was pale yellow and had a nub count of 1,487 nubs perpound of yarn. A control yarn containing only the antistatic additive ofExample 2 was produced and had a nub count of 5,362 nubs per pound ofyarn.

EXAMPLE 9 The procedure of Examaple 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 2 was used together with2.7 grams of octadecyl-3- (3,5-di-tertiarybutyl-4-hydroxyphenyl)propionate. The fiber produced was pale yellow andhad a nub count of 982 nubs per pound of yarn.

EXAMPLE 10 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 2 was used together with1.35 grams of tetra[- methylene3-(3,5-di-tertiary-butyl-4-hydroxyphenyDpropionatelmethane and 1.35grams of distearyl thiodiproprionate. The fiber produced was pale yellowand has a nub count of 1,405 nubs per pound ofyarn. 7

EXAMPLE 11 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 3 was used together with2.7 grams of tetra[methylene3-(3',5'-di-tertiary-butyl-4'-hydroxyphenyl)propionateJmethane. Thefiber produced was pale yellow and had a nub count of 1,475 nubs perpound of yarn.

EXAMPLE 12 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 3 was used together with2.7 grams of octadecyl-3- (3,5'-di-tertiarybutyl-4-hydroxyphenyl)propionate. The fiber produced was pale yellow andhad a nub count of 1,150 nubs per pound of yarn.

EXAMPLE 13 The procedure of Example 4 (Yarn A) was followed exceptthatgrams of the antistatic additive of Example 3 was used together with1.35 grams of tetra[- methylene3-(3,5-di-tertiary-butyl-4-hydroxyphenyl)propionatelmethane and 1.35grams of distearylthiodipropionate. The fiber produced was pale yellowand a nub count of 1,418 nubs per pound of yarn.

EXAMPLE 14 The procedure of Example 1 was followed except that 300 gramsof Tetronic 1504 was used together with 3.26 grams of dimethylterephthalate, a molar ratio of 1 to 0.7.

The antistatic additive produced was a soft solid having a meltviscosity of 1,300 centipoises at 100C., measured with the Brookfieldviscometer.

EXAMPLE 15 The procedure of Example 1 was followed except that 300 gramsof Tetronic 1504 was used together with 4.66 grams of dimethylterephthalate, a molar ratio of 1.0.

The antistatic additive produced was a soft solid having a meltviscosity of 17.500 centipoises at 100C., measured with the Brookfieldviscometer.

EXAMPLE 16 The procedure of Example 2 was followed except that 300 gramsof Tetronic 1504 was used together with 4.41 grams of the diisocyanatecompound of Ex ample 2, a molar ratio of l to 0.7.

The antistatic additive produced was a soft solid having a meltviscosity of 2, 1 50 centipoises at 100C., measured with the Brookfieldviscometer.

EXAMPLE 17 The procedure of Example 2 was followed except that 300 gramsof Tetronic 1504 was used together with 6.3 grams of the diisocyanatecompound of Example 2, a molar ratio of 1.

The antistatic additive produced was a soft solid having a meltviscosity of 17,200 centipoises at 100C., measured with the Brookfieldviscometer.

EXAMPLE 18 EXAMPLE 19 The procedure of Example 4 (Yarn A) was followedexcept that grams of the antistatic additive of Example 15 was usedtogether with 2.7 grams of tetra[- methylene3-(3,5'-di-tertiary-butyl-4'-hydroxyphenyl)propionatelmethane. The fiberproduced was pale yellow and had a nub count of 1,648 nubs per pound ofyarn.

A control yarn containing only the antistatic additive of Example 15 wasproduced and had a nub count of 5,451 nubs per pound of yarn.

EXAMPLE 20 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 17 was used together with2.7 grams of tetra[- methylene phenyl)propionatejmethane. The fiberproduced was pale yellow and had a nub count of 2,086 nubs per pound ofyarn.

A control yarn containing only the antistatic additive 'of Example 17was produced and had a nub count of 5,173 nubs per pound of yarn.

EXAMPLE 21 The procedure of Example 1 was followed except that 300 gramsof the Tetronic 1508 (molecular weight 27,000) was used together with1.95 grams ofdimethyl terephthalate (a molar ratio of l to 0.9).

The antistatic agent produced was a soft solid having a melt viscosityof 18.360 centipoises at C. measured with a Brookfield viscometer. Theviscosity ofthe original Tetronic 1508 was 6.400 centipoises at 100C.

EXAMPLE 22 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 21 was used together with2.7 grams of tetra[- methylene 3-(3,5-di-tertiary-butyl-4-hydroxyphenyl)propionatelmethane. The fiber produced was pale yellow and had anub count of'1,608 nubs per pound of yarn.

A control yarn containing only the antistatic additive of Example 21 wasproduced and had a nub count of 5,771 nubs per pound of yarn.

EXAMPLE 23 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 21 was used together with2.7 grams of octadecyl-3- (3',5-di-tertiarybutyl-4-hydroxyphenyl)propionate. The fiber produced was pale yellow andhad a nub count of 1,287 nubs per pound of yarn.

EXAMPLE 24 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 21 was used together with1.35 grams of tetra[- methylene3-(3,5'-di-tertiary-butyl-4-hydroxyphenyl)propionate1methane and 1.35grams of distearylthiodipropionate. The fiber produced was pale yellowand had a nub count of 1,563 nubs per pound of yarn.

EXAMPLE 25 EXAMPLE 26 The procedure of Example 1 was followed exceptthat 300 grams of Tetronic 901 (molecular weight 4,750) was usedtogether with 1 1.1 grams of dimethyl tercphthalate. The antistaticcompound produced was a soft solid having a melt viscosity of 4,300centipoises at 100C., measured with the Brookfield viscometer. Theviscosity of the original Tetronic 901 was 67 centipoises at 100C.

EXAMPLE 27 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 26 was used together with2.7 grams tetra[methylene 3-(3,5'-di-isopropyl4-hydroxypheny1)propionatelmethane. The fiber produced was pale yellowand had a nub count of 1,832 nubs per pound of yarn.

A control yarn was made with only the antistatic additive of Example 26.The yarn had a nub count of 7,315 nubs per pound.

EXAMPLE 28 The procedure of Example 4 (Yarn A) was followed 1 exceptthat grams of the antistatic additive of Example 26 was used togetherwith 2.7 grams of octadecyl-3-(3,5'-diisopropyl-4hydroxyphenyl)propionate. The fiber produced was paleyellow and had a nub count of 1,371 nubs per pound of yarn.

EXAMPLE 29 The procedure of Example 1 was followed except that 300 gramsof Tetronic 1307 (molecular weight 18,600) was used together with 2.82grams of dimethylterephthalate (a molar ratio of 1 to 0.9). Theantistatic agent produced was a waxy solid having a melt viscosity of18,700 centipoises at C. The viscosity of the original Tetronic 1307 at100C. was 1,220 centipoises.

EXAMPLE 30 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 29 was used together with2.7 grams of tetra[- methylene3-(3',5-di-tertiary-butyl-4'-hydroxyphenyl)propionate]methane. The fiberproduced was pale yellow and had a nub count of 1,518 nubs per pound ofyarn.

A control yarn was made with only the antistatic additive of Example 29and no'phenol compound. The yarn had a nub count of 4,560 nubs per poundof yarn.

EXAMPLE 3] The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 29 was used together with2.7 grams of octadecyl-3- 3,,5'-di-tertiarybutyl-4'-hydroxyphenyl)propionate. The fiber produced was pale yellowand had a nub count of 1,310 nubs per pound of yarn.

EXAMPLE 32 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 29 was used together with1.35 grams of tetra[- methylene3-(3,5-di-tertiary-butyl-4-hydroxyphenyl)propionate]methane and 1.35grams of distearylthiodipropionate. The fiber produced was pale yellowand had a nub count of 1,165 nubs per pound of yarn.

EXAMPLE 33 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example l was used together with0.9 gram of tetra[methylene3-(3',5-di-tertiary-butyl-4-hydroxyphenyl)propionate]methane. The fiberproduced was pale yellow and had a nub count of 1,950 nubs per pound ofyarn.

EXAMPLE 34 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example l was used together with1.8 grams of tetra[methylene3-(3,5'-di-tertiary-buty1-4-hydroxyphenyl)propionatelmethane. The fiberproduced was pale yellow and had a nub count of 1,720 nubs per pound ofyarn.

EXAMPLE EXAMPLE 36 The procedure of Example 4 (Yarn A) was followedexcept that 90 grams of the antistatic additive of Example l was usedtogether with 4.5 grams of tetra[methylene3-(3',5'-di-tertiary-butyl-4-hydroxyphenyl)propionatelmethane. The fiberproduced was pale yellow and had a nub count of 1,330 nubs per pound ofyarn.

EXAMPLE 37 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example l was used together with5.4 grams of tetra[methylene3-(3,5-di-tertiary-butyl-4-hydroxyphenyl)propionate]methane. The fiberproduced was pale yellow and had a nub count of 1,682 nubs per pound ofyarn.

EXAMPLE 38 The procedure of Example 4 (Yarn A) was followed except that60 grams of the antistatic additive of Example l was used together with1.8 grams of tetra[methylene3-(3',5-di-tertiary-butyl-4-hydroxypheny1)propionate]methane. The fiberproduced was pale yellow and had a nub count of 1,250 nubs per pound ofyarn.

A control yarn containing only the antistatic additive was produced andhad a nub count of 3,780 nubs per pound of yarn.

EXAMPLE 39 EXAMPLE 40 The procedure of Example 4 (Yarn A) was followedexcept that 30 grams of the antistatic additive of Example l was usedtogether with 0.9 gram of tetra[methylene3-(3'.5'-di-tertiary-butyl-4-hydroxyphenyl)propionate]methane. The fiberproduced was pale yellow and had a nub count of 851 nubs per pound ofyarn.

A control yarn conttaining only the antistatic additive was produced andhad a nub count of 3.265 nubs per pound of yarn.

EXAMPLE 41 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 4 was used together with1.35 grams of octadecyl-3- (3,5'-di-tertiarybutyl-4'-hydroxyphenyl)propionate and 1.35 grams ofdistearylthiodipropinate. The fiber produced was pale yellow and had anub count of 1,100 nubs per pound of yarn.

EXAMPLE 42 The procedure of Example 4 (Yarn A) was followed except that90 grams ofthe antistatic additive of Example 1 was used together with0.45 gram oftetra[methylene3-(3,5'-di-tertiary-butyl-4'-hydroxyphenyl)propionate]methane. The fiberproduced was pale yellow and had a nub count of 2,125 nubs per pound ofyarn.

EXAMPLE 43 The procedure of Example 4 (Yarn A) was followed except that90 grams of the antistatic additive of Example 1 was used together with7.2 grams oftetra[methylene3-(3,5'-di-tertiary-butyl-4'-hydroxyphenyl)propionate]methane. The fiberproduced was pale yellow and had a nub count of 1,650 nubs per pound ofyarn.

EXAMPLE 44 Polycaproamide pellets containing the antistatic agent ofExample 1 and tetra[methylene3-(3',5-ditertiary-butyl-4-hydroxyphenyl)propionatelmethane wereprepared in accordance with the procedure of Example 4 (Yarn A). Thepolycaproamide pellets were melted at about 285C. and then melt extrudedunder pressure of 15 psig to a orifice spinnerette, each of the orificeshaving a diameter of0.018 inch to produce a 4,500 denier fiber. Thefiber was collected at 1,000 feet per minute and was drawn about 4 timesthe extruded length to produce 1,125 denier yarn. This yarn isparticularly useful in the production of carpets as indicated in thefollowing testing procedures.

The yarn was textured using a steam jet and then twoplied. This yarn wastufted into a level loop carpet at 6.5 stitch rate, 910/32 inch pileheight, mock dyed and latexed. Static buildup of the carpet was testedby a shuffle test" measuring the electrostatic voltage buildup on aperson walking with a series of short shuffling steps on a piece ofcarpet conditioned at 70F. at 20% relative humidity. The voltagegenerated was 4.8 KV.

The untextured yarn was also tested for nubs using the nub countprocedure of Example 5 except that the ceramic cleaner gap used had anopening of 0.006 inch. The nub count of the yarn was 1 00 nubs perpound.

A control yarn made with no additives had a nub count of nubs per pound,but carpet made with the control yarn generated a voltage of 14.1 KV inthe above-described shuffle test.

EXAMPLE 45 The procedure of Example 44 was repeated except that thepolycaproamide pellets were made with the antistatic agent of Example 1and octadecyl-3-(3',5-ditertiary butyl-4-hydroxyphenyl)propionate. Thenub count of the resulting yarn was 102 nubs per pound. Carpet made withthe yarn generated a voltage of 4.9 KV in the above-described shuffletest.

DlSCUSSlON In additional tests it was determined that the molecularweight of the tetrol compound used to prepare the No. 3,657,386. Byfiber is meant multifilament yarn, monofilament, and all the knownphysical forms of synthetic fibers. By polyamide is meant the polymersmade by condensation of diamines with dibasic acids or 16 theimprovement comprising dissolving in the extrudate prior to extrusion atleast 0.1 percent by weight, based on the weight of the antistaticcompound, of a phenol compound selected from the group consisting bypolymerization of lactams or amino acids, resulting of: in a syntheticresin characterized by the recurring group CONH--. By ethylene oxidemoiety is (lower) alky meant the portion of the chemical molecule -(CHC- 0 H O).

Desirably, the chain-extended antistatic compound H0 (c -c-0- (c )-H andthe other additives are substantially uniformly dispersed in thepolyamide. Preferably, the sulfur compound is used together with thephenol compound, and the weight ratio ofthe phenol compound to sulfurcom- (lower) alkyl pound is preferably between 0.25 and 4.0.

in which has a value of from 1 to 6 and y has a value EXAMPLE 46 of from6 to 30; and The procedure of Example 4 (Yarn A) was repeated exceptthat the additives, i.e., 2.7 grams of tetra[methy- R R lene3-(3',5-di-tertiary-butyl 4 -hydroxyphenyl)pro- 2O c pionate]methane and90 grams of the antistatic compound of Example 1 were charged to theglass reactor R with the e-caprolactam and aminocaproic acid. The fiberproduced was pale yellow and had a nub count of in which R is l,585 nubsper pound of yarn. Yarn prepared in a-similar way containing only theantistatic additive contained 6,030 nubs per pound of yarn. (lower)alkyl 0 EXAMPLE 47 Procedure and additives were similar to Example 4 Hog x' 2 ;.v (Yarn A) except the polyamide was polymerized from poly(hexamethylammonium adipate salt. A fiber was I produced and nubscounted as in Example 5, and the (lower) alkyl result was 1,512 nubs perpound of yarn. A second yarn, similarly prepared with the antistaticadditive and wherein has a value from l to 6 and y has a value noadditional additive, contained 5,625 nubs per pound of l to 6. of yarn.2. The process ofclaim 1 wherein 0.5 to 8 percent by We claim: weight ofthe phenol compound is incorporated into 1. In a process for theformation of an antistatic polythe fiber. based on the weight of theantistatic comamide fiber from a fiber-forming polyamide polymer pound.containing about 1 to 12 percent by weight of an anti- 3. The process ofclaim 2 additionally comrising disstatic compound which is achain-extended reaction solving in the extrudate prior to extrusion atleast 0.1% product of a tetrol compound represented by the forby weight,based on the weight of the antistatic addimula: tive, of a sulfurcompound of the formula:

V 9 3 e 3 (OCH CH (0CHCI-I (cn cnm tca cn m a e3 NAN on v I 3 H (OCH CHe (OCHCH f (CH CHO) g (CH CH O) H where a, b, c, z1,e.f, g, and hareeach a whole number and A is a difunctional radical from a hydrocarboncontaining l to 13 carbon atoms, said tetrol compound having a molecularweight between about 4,000 and about 50,000 and at least one compoundselected from the group consisting of compounds which yield thefollowing divalent radical:

ivhere A is a difunctional radical from a hydrocarbon :ontaining l to 30carbon atoms, by extruding the molen polymer through an orifice into aquenching melium and thereafter stretching the resulting filaments,

2n COOR" S tc a cooR" where R" is alkyl radical containing 8 to 18carbon 17 methylene3-(3',5'-di-tertiary-butyl-4'-hydroxyphenyl)propionatc1methane andoctadecyl-3-( 3,5-ditertiary butyl-4-hydroxyphenyl)propionate.

6. An antistatic fiber consisting essentially of polyamide and about Ito 12 percent by weight of an antistatic compound which is achain-extended reaction product of a tetrol compound represented by theformula:

in which R is H (OCH CH a (OCHCH (CH CHO) (CH CH O) H (3H N-A-N where a,b, c, (1, e,f, g and h are each a whole number and A is a difunctionalradical from a hydrocarbon containing l to 13 carbon atoms, said tetrolcompound having a molecular weight between about 4,000 and about 50,000and at least one compound selected from the group consisting ofcompounds which yield the following divalent radical:

where A is a difunctional radical from a hdyrocarbon containing 1 to 30carbon atoms; and at least 0.] percent by weight, based on the weight ofthe antistatic compound, of a phenol compound selected from the groupconsisting of (lower) alkyl HO y l (lower) alkyl in which .t has a valueof from I to 6 and y has a value of from 6 to 30, and

(CH CI-IO) (CH CH O) H (lower) alkyl H0 CH c 0 (CH )y (lower) alkylwherein has a value from 1 to 6 and y has a value of l to 6.

7. The fiber of claim 6 wherein 0.5 to 8 percent by weight of the phenolcompound is incorporated into the fiber based on the weight of theantistatic compound.

8. The fiber of claim 7 additionally consisting of at least 0.1% byweight, based on the weight of the antistatic additive, of a sulfurcompound of the formula:

/ (c COOR" s\ (C H COOR" UNITED STATES PATENT AND TRADEMARK OFFICECERTIFICATE OF CORRECTION PATENT NO. ,6 9 DATED March 25, 1975 VENTOR(S)I Lamberto Crescentini and Rodney Lee Wells It is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

Q Column 1, line 27, "oxideethylene" should read -oxide-ethylene-. 1

Column 1, line 65, "selections" should read -sections-.

Q Column 1, line 66 "dimeters" should read diameters -r.

Column 6, line 7, "additional" should read addition---. A I

' Column 6, line 32, "chain extended" should read" -'chainextended-.

Column 8, line 10, "wellknown" should read --wellknown- Column 14, line35, "910/32" should read --910. 32--.

. Signed and Scaled this eighteenth D ay Of November 1 9 75 [SEAL]Arrest.

RUTH C. MASON C. MARSHALL DANN :I H X Uffifl Commissioner HIIUHIHS andTrademarks

1. IN A PROCESS FOR THE FORMATION OF AN ANTISTATIC POLYAMIDE FIBER FROMA FIBER-FORMING POLYAMIDE POLYMER CONTAINING ABOUT 1 TO 12 PERCENT BYWEIGGHT OF AN ANTISTATIC COMPOUND WHICH IS A CHAIN-EXTENDED REACTIONPRODUCT OF A TETROL COMPOUND REPRESENTED BY THE FORMULA
 2. The processof claim 1 wherein 0.5 to 8 percent by weight of the phenol compound isincorporated into the fiber, based on the weight of the antistaticcompound.
 3. The process of claim 2 additionally comrising dissolving inthe extrudate prior to extrusion at least 0.1% by weight, based on theweight of the antistatic additive, of a sulfur compound of the formula:4. The process of claim 3 wherein the weight ratio of the phenolcompound to the sulfur compound is between 0.25 and 4.0.
 5. The processof claim 4 wherein the phenol compound is selected from the groupconsisting of tetra(methylene 3-(3'',5''-di-tertiary-butyl-4''-hydroxyphenyl)propionate)methane andoctadecyl-3-(3'' ,5''-di-tertiary butyl-4''-hydroxyphenyl)propionate. 6.An antistatic fiber consisting essentially of polyamide and about 1 to12 percent by weight of an antistatic compound which is a chain-extendedreaction product of a tetrol compound represented by the formula:
 7. Thefiber of claim 6 wherein 0.5 to 8 percent by weight of the phenolcompound is incorporated into the fiber based on the weight of theantistatic compound.
 8. The fiber of claim 7 additionally consisting ofat least 0.1% by weight, based on the weight of the antistatic additive,of a sulfur compound of the formula:
 9. The fiber of claim 8, whereinthe weight ratio of the phenol compound to the sulfur compound isbetween 0.25 and 4.0.
 10. The fiber of claim 9 wherein the phenolcompound is selected from the group consisting of tetra(methylene3-(3'', 5''-di-tertiary-butyl-4''-hydroxyphenyl)propionate)methane andoctadecyl-3-(3'' ,5''-di-tertiary butyl-4''-hydroxyphenyl) propionate.